Cyclohexenones and their use for controlling undesirable plant growth

ABSTRACT

Cyclohexenones of the formula   &lt;IMAGE&gt;   where R1 is alkyl, R2 is alkyl, alkenyl, alkynyl, or haloalkyl, Z is hydrogen or alkoxycarbonyl, and X is a substituted or unsubstituted pentamethylene chain in which one or two methylene groups can be replaced by O, S, SO, SO2 or NR3, and their use for controlling undesirable plant growth.

The present invention relates to cyclohexenones, their preparation, andherbicides which contain these compounds as active ingredients.

Japanese Preliminary Published Applictions Nos. 82/183 746 and 83/144384 disclose that spirocyclic cyclohexenones possess herbicidalactivity.

We have found that cyclohexenones of the formula ##STR2## wherein R¹ isC₁ -C₄ -alkyl, R² is C₁ -C₄ -alkyl, C₃ -C₅ -alkynyl or unsubstituted orhalogen-substituted C₃ -C₅ -alkenyl, Z is hydrogen or C₂ -C₅-alkoxycarbonyl and X is a pentamethylene chain which is unsubstitutedor substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylthio andin which one or two methylene groups may be replaced by O, S, SO, SO₂ orNR³, where R³ is C₁ -C₄ -alkyl, C₂ -C₇ -acyl or benzyl, with the provisothat one substituent from the group consisting of alkyl, alkoxy andalkylthio is present when X is pentamethylene, and the crop-toleratedsalts of these compounds, exhibit a good herbicidal action, preferablyagainst species from the grasses famil (Gramineae). They are toleratedby, and hence have a selective action in, broad-leaved crops and inmonocotyledon crops which do not belong to the Gramineae.

The cyclohexenones of the formula I can occur in tautomeric forms, allof which are embraced by the claims: ##STR3## In formula I, R¹ isstraight-chain or branched C_(1-C) ₄ -alkyl eg. methyl, ethyl, n-propyl,sec-butyl or isobutyl, R² is straight-chain or branched C₁ -C₄ -alkyl,C₃ -C₅ -alkynyl or unsubstituted or halogen-substituted, in particularchlorine-substituted, C₃ -C₅ -alkenyl, eg. ethyl, propyl, allyl,propargyl, 3-chloroallyl (cis or trans) or 2-chloroallyl, Z is hydrogenor C₂ -C₅ -alkoxycarbonyl, eg. methoxycarbonyl or ethoxycarbonyl, and Xis a pentamethylene chain in which one or two methylene groups can bereplaced by O, S, SO, SO₂ or NR³. This radical may be unsubstituted orsubstituted by one or more radicals from the group consisting of C₁ -C₄-alkyl, C₁ -C₄ -alkoxy and C₁ -C₄ -alkylthio, eg. methyl, ethyl,n-propyl, sec-butyl, isobutyl, methoxy, ethoxy, n-propoxy, n-butoxy,methylthio, ethylthio, isopropylthio or sec-butylthio. If X ispentamethylene, a substituent from the group consisting of alkyl, alkoxyand alkylthio must be present. In NR³, R³ is C₁ -C₄ -alkyl, C₂ -C₇ -acylor benzyl, eg. methyl, ethyl, acetyl, propionyl, benzoyl or benzyl. Xis, for example, ##STR4##

Examples of suitable salts of the cyclohexenones of the formula I arethe alkali metal salts, in particular the potassium or sodium salts,alkaline earth metal salts, in particular calcium salts, magnesium saltsor barium salts, manganese salts, copper salts, zinc salts and ironsalts, as well as ammonium, phosphonium, sulfonium and sulfoxoniumsalts, for example ammonium, tetraalkylammonium, benzyltrialkylammonium,trialkylsulfonium, or trialkylsulfoxonium salts.

Preferred cyclohexenones of the formula I are those in which Z ishydrogen, or those in which X is an oxapentamethylene orthiapentamethylene chain.

The compounds of the formula I can be obtained by reacting a compound ofthe formula ##STR5## where R¹, Z and X have the above meanings, with ahydroxylamine derivative R² O--NH₃ Y, where R² has the above meaningsand Y is an anion.

The reaction is advantageously carried out in the heterogeneous phase inan inert diluent at from 0° to 80° C. or from 0° C. to the boiling pointof the reaction mixture, in the presence of a base. Examples of suitablebases are carbonates, bicarbonates, acetates, alcoholates, hydroxidesand oxides of alkali metals and alkaline earth metals, in particular ofsodium, potassium, magnesium and calcium. Organic bases, such aspyridine or tertiary amines, can also be used.

The reaction takes place particularly readily at a pH of from 2 to 9, inparticular from 4.5 to 5.5, the pH advantageously being set by adding anacetate, for example an alkali metal acetate, in particular sodiumacetate or potassium acetate or a mixture of the two salts. Alkali metalacetates are added in amounts of, for example, from 0.5 to 2 moles,based on the ammonium compound of the formula R² O--NH₃ Y.

Examples of suitable solvents are dimethyl sulfoxide, alcohols, such asmethanol, ethanol or isopropanol, benzene, hydrocarbons andchlorohydrocarbons, such as chloroform, dichloroethane, hexane orcyclohexane, esters, such as ethyl acetate, and ethers, such as dioxaneor tetrahydrofuran.

The reaction is complete after a few hours, and the product can then beisolated by evaporating down the mixture, adding water, extracting witha non-polar solvent, such as methylene chloride, and distilling off thesolvent under reduced pressure.

The compounds of the formula I can furthermore be obtained by reacting acompound of the formula II with a hydroxylamine of the formula R²O--NH₂, where R² has the above meanings, in an inert diluent at from 0°C. to the boiling point of the reaction mixture, in particular from 15°to 70° C. If necessary, the hydroxylamine can be used in the form of anaqueous solution.

Examples of suitable solvents for this reaction are alcohols, such asmethanol, ethanol, isopropanol or cyclohexanol, hydrocarbons andchlorohydrocarbons, such as hexane, cyclohexane, methylene chloride,toluene or dichloroethane, esters, such as ethyl acetate, nitriles, suchas acetronitrile, and cyclic ethers, such as tetrahydrofuran.

The compounds of the formula I can also be obtained by reacting acompound of the formula II with an unsubstituted hydroxylammonium saltNH₂ OH.HY, where Y has the above meaning, with the addition of a solventand an auxiliary base, at from 0° to 80° C., to give an oxime of theformula ##STR6## where R¹, X and Z have the above meanings, and furtherreacting this product with an alkylating agent of the formula R² Y',where R² has the above meanings and Y' is a leaving group.

Suitable solvents are those listed for the reaction of the compounds ofthe formula II with hydroxylamines, and suitable bases are the basicsubstances stated for the reaction of the compounds of the formula IIwith hydroxylamine derivatives of the formula R² O--NH₃ Y, twice theamount of base being required in this case.

The alkali metal salts of the compounds of the formula I can be obtainedby treating these compounds with sodium hydroxide or potassium hydroxidein aqueous solution or in an organic solvent, such as methanol, ethanolor acetone. Sodium alcoholates and potassium alcoholates can also beused as bases.

The remaining metal salts, eg. the manganese, copper, zinc, iron,calcium, magnesium and barium salts can be prepared from the sodiumsalts by reaction with the corresponding metal chlorides in aqueoussolution. Ammonium and phosphonium salts can be obtained by reactingcompounds of the formula I with ammonium, phosphonium, sulfonium orsulfoxonium hydroxides, if appropriate in aqueous solution.

The compounds of the formula II can be prepared fromcyclohexane-1,3-diones of the formula IV by a conventional method(Tetrahedron Lett. 29, (1975), 2491), the said cyclohexane-1,3-dionesalso occurring in the tautomeric form IV a ##STR7##

It is also possible to prepare compounds of the formula II via theenol-ester intermediates, which are obtained in the reaction ofcompounds of the formula IV and undergo rearrangement in the presence ofan imidazole or pyridine derivative (Japanese Preliminary PublishedApplication No. 79/063052).

The compounds of the formula IV are obtained by conventional processes,as can be seen from the equation below:

The Example which follows illustrates the preparation of thecyclohexenones of the formula I.

EXAMPLE

9.7 parts by weight of 9-butyryl-3-oxaspiro[5.5]undecane-8,10-dione aretaken up in 100 parts by volume of ethanol, and 3.57 parts by weight ofsodium bicarbonate are added. After the addition of 4.13 parts by weightof ethoxyaminohydrochloride, the reaction mixture is stirred for about20 hours at 20° C. and then poured into ice water/methylene chloride,and the organic phase is separated off and evaporated down. 10.9 partsby weight of9-(1-ethoxyimino-n-butyl)-3-oxaspiro[5.5]undecane-8,10-dione of meltingpoint 74°-76° C. remain (compound No. 1).

The following cyclohexenone derivatives of the formula I can be preparedby the same route:

    __________________________________________________________________________    Compound                                                                      no.   X                Z      R.sup.1                                                                            R.sup.2    M.p.[°C.]/n.sub.D                                                      (°C.)/.sup.1 H--NMR                                                    data                            __________________________________________________________________________     1    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                          74-76                            2    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  allyl      1.5317 (22)                      3    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                           COOCH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                             4    CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                             5    CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  allyl                                       6    CH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                          1.5522 (22)                      7    CH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2                                                           COOC.sub.2 H.sub.5                                                                   n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                             8    CH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  allyl      1.5572                           9    CH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  3-chloroallyl (trans)                                                                    1.5657                          10    CH.sub.2 SOCH.sub.2 CH.sub.2 CH.sub.2                                                          H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            11    CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                   H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            12    CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                   H      n-C.sub.3 H.sub.7                                                                  allyl                                      13    CH.sub.2 CH(SEt)CH.sub.2 CH.sub.2 CH.sub.2                                                     H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                          0.95 (t, 3H); 1.2 (t, 3H);                                                    1.32 (t, 3H); 2.53 (q,                                                        2H);                                                                          2.9 (t, 2H); 4.1 (q, 2H);                                                     15 (s, 1H)                      14    CH.sub.2 CH(SEt)CH.sub.2 CH.sub.2 CH.sub.2                                                     H      n-C.sub.3 H.sub.7                                                                  allyl      0.95 (t, 3H); 1.2 (t, 6H),                                                    2.9 (t, 2H), 4.5 (d, 2H),                                                     5.35 (dd, 2H); 5.9-6.1 (m,                                                    1H)                             15    CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            16    CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub. 7                                                                 allyl                                      17    CH.sub.2 CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.2                                                H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            18    CH.sub.2 SCH.sub.2 SCH.sub.2                                                                   H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                          76-80                           19    CH.sub.2 SCH.sub.2 SCH.sub.2                                                                   H      C.sub.2 H.sub.5                                                                    allyl      1.5954 (22)                     20    CH.sub.2 SCH.sub.2 SCH.sub.2                                                                   H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                          80-82                           21    CH.sub.2 SCH.sub.2 SCH.sub.2                                                                   H      n-C.sub.3 H.sub.7                                                                  allyl      62-64                           22    CH.sub.2 SCH.sub.2 SCH.sub.2                                                                   H      C.sub.2 H.sub.5                                                                    3-chloroallyl (trans)                      23    CH.sub.2 SCH.sub.2 SCH.sub.2                                                                   H      n-C.sub.3 H.sub.7                                                                  3-chloroallyl (trans)                      24    CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                          1.5508 (23)                     25    CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  3-chloroallyl (trans)                      26    CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  allyl      1.5558 (23)                     27    CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        28    CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        29    CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            30    CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    allyl                                      31    CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        32    CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        33    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        34    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        35    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            36    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    allyl                                      37    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        38    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        39    CH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        40    CH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub. 5                           41    CH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    allyl                                      42    CH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        43    CH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        44    SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            45    SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  allyl                                      46    SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        47    SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        48    SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            49    SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    allyl                                      50    SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        51    SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        52    CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                           H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        53    CH.sub. 2 CH.sub.2 SCH.sub.2 CH.sub.2                                                          H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        54    CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            55    CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    allyl                                      56    CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        57    CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                           H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        58    CH.sub.2 OCH.sub.2 OCH.sub.2                                                                   H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            59    CH.sub.2 OCH.sub.2 OCH.sub.2                                                                   H      n-C.sub.3 H.sub.7                                                                  allyl                                      60    CH.sub.2 OCH.sub.2 OCH.sub.2                                                                   H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        61    CH.sub.2 OCH.sub.2 OCH.sub.2                                                                   H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        62    CH.sub.2 OCH.sub.2 OCH.sub.2                                                                   H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            63    CH.sub.2 OCH.sub.2 OCH.sub.2                                                                   H      C.sub.2 H.sub.5                                                                    allyl                                      64    CH.sub.2 OCH.sub.2 OCH.sub.2                                                                   H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        65    CH.sub.2 OCH.sub.2 OCH.sub.2                                                                   H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        66    CH.sub.2 SCH.sub. 2 SCH.sub.2                                                                  H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        67    CH.sub.2 SCH.sub.2 SCH.sub.2                                                                   H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        68    CH.sub.2 SCH.sub.2 SCH.sub.2                                                                   H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        69    CH.sub.2 SCH.sub.2 SCH.sub.2                                                                   H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        70    CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            71    CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  allyl                                      72    CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        73    CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        74    CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            75    CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    allyl                                      76    CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        77    CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        78    CH.sub.2 CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            79    CH.sub.2 CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  allyl                                      80    CH.sub.2 CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        81    CH.sub.2 CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        82    CH.sub.2 CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            83    CH.sub.2 CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    allyl                                      84    CH.sub.2 CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        85    CH.sub.2 CH.sub.2 CH(OCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        86    CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            87    CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  allyl                                      88    CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub. 3 H.sub.7                                                                 3-Cl--allyl (trans)                        89    CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        90    CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            91    CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    allyl                                      92    CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        93    CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        94    CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            95    CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  allyl                                      96    CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        97    CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        98    CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            99    CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub. 2 CH.sub.2                                              H      C.sub.2 H.sub.5                                                                    allyl                                      100   CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        101   CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        102   CH.sub.2 CH(SCH.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                      H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        103   CH.sub.2 CH(SCH.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                      H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        104   CH.sub.2 CH(SCH.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                      H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            105   CH.sub.2 CH(SCH.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                      H      C.sub.2 H.sub.5                                                                    allyl                                      106   CH.sub.2 CH(SCH.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                      H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        107   CH.sub.2 CH(SCH.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                      H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        108   CH.sub.2 CH(SOCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                              H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            109   CH.sub.2 CH(SOCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                              H      n-C.sub.3 H.sub.7                                                                  allyl                                      110   CH.sub.2 CH(SOCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                              H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        111   CH.sub.2 CH(SOCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                              H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        112   CH.sub.2 CH(SOCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                              H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            113   CH.sub.2 CH(SOCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                              H      C.sub.2 H.sub.5                                                                    allyl                                      114   CH.sub.2 CH(SOCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                              H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        115   CH.sub.2 CH(SOCH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                              H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        116   CH.sub.2 CH(SO.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                       H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            117   CH.sub.2 CH(SO.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                       H      n-C.sub.3 H.sub.7                                                                  allyl                                      118   CH.sub.2 CH(SO.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                       H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        119   CH.sub.2 CH(SO.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                       H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        120   CH.sub.2 CH(SO.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                       H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            121   CH.sub.2 CH(SO.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                       H      C.sub.2 H.sub.5                                                                    allyl                                      122   CH.sub.2 CH(SO.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                       H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        123   CH.sub.2 CH(SO.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                       H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        124   CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            125   CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  allyl                                      126   CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        127   CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        128   CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            129   CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    allyl                                      130   CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        131   CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        132   CH.sub.2 CH.sub.2 N(COC.sub.6 H.sub.5)CH.sub.2 CH.sub.2                                        H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                          83-85                           133   CH.sub.2 CH.sub.2 N(COC.sub.6 H.sub.5)CH.sub.2 CH.sub.2                                        H      n-C.sub.3 H.sub.7                                                                  allyl                                      134   CH.sub.2 CH.sub.2 N(COC.sub.6 H.sub.5)CH.sub.2 CH.sub.2                                        H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        135   CH.sub.2 CH.sub.2 N(COC.sub.6 H.sub.5)CH.sub.2 CH.sub.2                                        H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        136   CH.sub.2 CH.sub.2 N(COC.sub.6 H.sub.5)CH.sub.2 CH.sub.2                                        H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            137   CH.sub.2 CH.sub.2 N(COC.sub.6 H.sub.5)CH.sub.2 CH.sub.2                                        H      C.sub.2 H.sub.5                                                                    allyl                                      138   CH.sub.2 CH.sub.2 N(COC.sub.6 H.sub.5)CH.sub.2 CH.sub.2                                        H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        139   CH.sub.2 CH.sub.2 N(COC.sub.6 H.sub.5)CH.sub.2 CH.sub.2                                        H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        140   CH.sub.2 CH.sub.2 N(COC.sub.6 H.sub.5)CH.sub.2 CH.sub.2                                        CO.sub.2 CH.sub.3                                                                    n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                          55-57° C.                141   CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2 CH.sub.2                                               CO.sub.2 CH.sub.3                                                                    n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                                                                          0.98 (t, 3H), 1.35 (t,                                                        3H),                                                                          1.47-1.74 (m, 6H), 2.09                                                       (s, 3H), 2.87-3.0 (m, 2H),                                                    3.32-3.6 (m, 2H),                                                             3.72 (s, 3H), 4.1 (q, 2H)       142   CH.sub.2 CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.5                            143   CH.sub.2 CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  allyl                                      144   CH.sub.2 CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2                                               H      n-C.sub.3 H.sub.7                                                                  3-Cl--allyl (trans)                        145   CH.sub.2 CH.sub. 2 CH(SCH.sub.3)CH.sub.2 CH.sub.2                                              H      n-C.sub.3 H.sub.7                                                                  methylallyl (trans)                        146   CH.sub.2 CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                            147   CH.sub.2 CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    allyl                                      148   CH.sub.2 CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    3-Cl--allyl (trans)                        149   CH.sub.2 CH.sub.2 CH(SCH.sub.3)CH.sub.2 CH.sub.2                                               H      C.sub.2 H.sub.5                                                                    methylallyl (trans)                        __________________________________________________________________________

The cyclohexenones of the formula I may be applied for instance in theform of directly sprayable solutions, powders, suspensions (includinghigh-percentage aqueous, oily or other suspensions), dispersions,emulsions, oil dispersions, pastes, dusts, broadcasting agents, orgranules by spraying, atomizing, dusting, broadcasting or watering. Theforms of application depend entirely on the purpose for which the agentsare being used, but they must ensure as fine a distribution of theactive ingredients according to the invention as possible.

For the preparation of solutions, emulsions, pastes and oil dispersionsto be sprayed direct, mineral oil fractions of medium to high boilingpoint, such as kerosene or diesel oil, further coal-tar oils, and oilsof vegetable or animal origin, aliphatic, cyclic and aromatichydrocarbons such as benzene, toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes and their derivatives suchas methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,etc., and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone, and water are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes,oil dispersions or wettable powders by adding water. To prepareemulsions, pastes and oil dispersions the ingredients as such ordissolved in an oil or solvent may be homogenized in water by means ofwetting or dispersing agents, adherents or emulsifiers. Concentrateswhich are suitable for dilution with water may be prepared from activeingredient, wetting agent, adherent, emulsifying or dispersing agent andpossibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid, naphthalenesulfonic acids,phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkylsulfonates, alkali metal and alkaline earth metal salts ofdibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcoholsulfates, alkali metal and alkaline earth metal salts of fatty acids,salts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof sulfated fatty alcohol glycol ethers, condensation products ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensation products of naphthalene or naphthalenesulfonic acids withphenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acid, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain flours, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % byweight of active ingredient.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 2 is mixed with 10 parts by weightof N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitablefor application in the form of very fine drops.

II. 20 parts by weight of compound no. 8 is dissolved in a mixtureconsisting of 80 parts by weight of xylene, 10 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into 100,000 parts by weight of water and uniformlydistributing it therein, an aqueous dispersion is obtained containing0.02% by weight of the active ingredient.

III. 20 parts by weight of compound no. 1 is dissolved in a mixtureconsisting of 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 7 moles of ethyleneoxide and 1 mole of isooctylphenol, and 10 parts by weight of the adductof 40 moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into 100,000 parts by weight of water and finely distributingit therein, an aqueous dispersion is obtained containing 0.02% by weightof the active ingredient.

IV. 20 parts by weight of compound no. 1 is dissolved in a mixtureconsisting of 25 parts by weight of cyclohexanol, 65 parts by weight ofa mineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil. By pouring the solution into 100,000 parts by weightof water and uniformly distributing it therein, an aqueous dispersion isobtained containing 0.02% by weight of the active ingredient.

V. 20 parts by weight of compound no. 2 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid,17 parts by weight of the sodium salt of a lignin-sulfonic acid obtainedfrom a sulfite waste liquor, and 60 parts by weight of powdered silicagel, and triturated in a hammer mill. By uniformly distributing themixture in 20,000 parts by weight of water, a spray liquor is obtainedcontaining 0.1% by weight of the active ingredient.

VI. 3 parts by weight of compound no. 9 is intimately mixed with 97parts by weight of particulate kaolin. A dust is obtained containing 3%by weight of the active ingredient.

VII. 30 parts by weight of compound no. 9 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

VIII. 20 parts of compound no. 6 is intimately mixed with 2 parts of thecalcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcoholpolyglycol ether, 2 parts of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate and 68 parts of a paraffinic mineraloil. A stable oily dispersion is obtained.

The active ingredients, or agents containing them, may be applied pre-or postemergence. If certain crop plants tolerate the active ingredientsless well, application techniques may be used in which the herbicidalagents are sprayed from suitable equipment in such a manner that theleaves of sensitive crop plants are if possible not touched, and theagents reach the soil or the unwanted plants growing beneath the cropplants (post-directed, lay-by treatment).

The amount of active ingredient applied depends on the time of the year,the plants to be combated and their growth stage, and varies from 0.025to 3 kg/ha and more, but is preferably from 0.1 to 0.5 kg/ha.

The action of the cyclohexenones of the formula I on plant growth isdemonstrated in greenhouse experiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³,and which were filled with a sandy loam containing about 1.5% humus. Theseeds of the test plants were sown shallow, and separately, according tospecies. For the preemergence treatment, the active ingredients wereapplied to the surface of the soil immediately after the seeds had beensown. The compounds are emulsified or suspended in water as vehicle, andsprayed through finely distributing nozzles. The application rate was3.0 kg of active ingredient per hectare. After the agents had beenapplied, the vessels were lightly sprinkler-irrigated to inducegermination and growth. Transparent plastic covers were then placed onthe vessels until the plants had taken root. The cover ensured uniformgermination of the plants, insofar as this was not impaired by theactive ingredients.

For the postemergence treatment, the plants were first grown in thevessels to a height of from 3 to 15 cm, depending on growth form, beforebeing treated. The soybean plants were grown in a peat-enrichedsubstrate. For this treatment, either plants which had been sowndirectly in the pots and grown there were selected, or plants which hadbeen grown from seedlings and were transplanted to the pots a few daysbefore treatment. The application rates for postemergence treatment were0.125 and 0.25 kg of active ingredient per hectare. No covers wereplaced on the vessels in this method.

The pots were set up in the greenhouse--species from warmer areas atfrom 20° to 35° C., and species from moderate climates at 10° to 25° C.The experiments were run for 2 to 4 weeks. During this period, theplants were tended and their reactions to the various treatmentassessed. The scale used for assessment was 0 to 100, 0 denoting nodamage or normal emergence, and 100 denoting nonemergence or completedestruction of at least the visible plant parts.

The plants used in the experiments were Avena fatua, Avena sativa,Digitaria sanguinalis, Echinochloa crus-galli, Glycine max., Hordeumvulgare, Lolium multi-florum, Oryza sativa, Setaria italica, and Sinapisalba.

For comparative purposes, herbicides were used which contained theactive ingredients3-(1-ethoxyimino-n-butyl)-spiro[5.5]-undecane-2,4-dione (A; JapaneseLaid-Open Application No. 82/183 746) or8-(1-ethoxyimino-n-butyl)-2-thiaspiro[4.5]-decane-7,9-dione (B; JapaneseLaid-Open Application No. 83/144 348).

Preemergence application

For instance compounds nos. 1, 2, 6, 8 and 9 proved to be herbicidallyeffective on plants from the grasses family, whereas Sinapis alba, as arepresentative of dicotyledonous plants, remained completely undamaged.

Postemergence application

On postemergence application of 0.125 kg/ha, for example compounds nos.1 and 2 combatted grassy plants better than comparative agent A;soybeans, as dicotyledonous crop plant, were not damaged. For instancecompounds nos. 6 and 8 are better tolerated than comparative agent B incombatting unwanted grasses in rice, a crop from the grasses family.

Significant problem weeds in soybeans can be better combatted withcompounds nos. 24 and 26 than with prior art active ingredient A, andthe broadleaved crop plant suffers no damage. Compounds nos. 20 and 21,for instance, are suitable for use against volunteer plants from theGraminease family, such as Sorghum bicolor and Zea mays, and againstimportant grassy weeds in soybeans. Comparative agent A has a farinferior herbicidal action.

In view of their spectrum of action, their tolerance by crop plants orthe desired influence on crop plant growth, and in view of the numerousapplication methods possible, the compounds according to the inventionmay be used in a large number of crop plants.

The following crops may be mentioned by way of example:

    ______________________________________                                        Botanical name      Common name                                               ______________________________________                                        Allium cepa         onions                                                    Ananas comosus      pineapples                                                Arachis hypogaea    peanuts (groundnuts)                                      Asparagus officinalis                                                                             asparagus                                                 Beta vulgaris spp. altissima                                                                      sugarbeets                                                Beta vulgaris spp. rapa                                                                           fodder beets                                              Beta vulgaris spp. esculenta                                                                      table beets, red beets                                    Brassica napus var. napus                                                                         rapeseed                                                  Brassica napus var. napobrassica                                                                  swedes                                                    Brassica napus var. rapa                                                                          turnips                                                   Brassica rapa var. silvestris                                                 Camellia sinensis   tea plants                                                Carthamus tinctorius                                                                              safflower                                                 Carya illinoinensis pecan trees                                               Citrus limon        lemons                                                    Citrus maxima       grapefruits                                               Citrus reticulata   mandarins                                                 Citrus sinensis     orange trees                                              Coffea arabica (Coffea canephora,                                                                 coffee plants                                             Coffea liberica)                                                              Cucumis melo        melons                                                    Cucumis sativus     cucumbers                                                 Cynodon dactylon    Bermudagrass in turf                                                          and lawns                                                 Daucus carota       carrots                                                   Elais guineensis    oil palms                                                 Fragaria vesca      strawberries                                              Glycine max         soybeans                                                  Gossypium hirsutum  cotton                                                    (Gossypium arboreum                                                           Gossypium herbaceum                                                           Gossypium vitifolium)                                                         Helianthus annuus   sunflowers                                                Helianthus tuberosus                                                                              Jerusalem artichoke                                       Hevea brasiliensis  rubber plants                                             Hordeum vulgare     barley                                                    Humulus lupulus     hops                                                      Ipomoea batatas     sweet potatoes                                            Juglans regia       walnut trees                                              Lactuca sativa      lettuce                                                   Lens culinaris      lentils                                                   Linum usitatissimum flax                                                      Lycopersicon lycopersicum                                                                         tomatoes                                                  Malus spp.          apple trees                                               Manihot esculenta   cassava                                                   Medicago sativa     alfalfa (lucerne)                                         Mentha piperita     peppermint                                                Musa spp.           banana plants                                             Nicothiana tabacum  tobacco                                                   (N. rustica)                                                                  Olea europaea       olive trees                                               Oryza sativa        rice                                                      Phaseolus lunatus   limabeans                                                 Phaseolus mungo     mungbeans                                                 Phaseolus vulgaris  snapbeans, green beans,                                                       dry beans                                                 Petroselinum crispum                                                                              parsley                                                   spp. tuberosum                                                                Picea abies         Norway spruce                                             Abies alba          fir trees                                                 Pinus spp.          pine trees                                                Pisum sativum       English peas                                              Prunus avium        cherry trees                                              Prunus domestica    plum trees                                                Prunus dulcis       almond trees                                              Prunus persica      peach trees                                               Pyrus communis      pear trees                                                Ribes sylvestre     redcurrants                                               Ribes uva-crispa    gooseberries                                              Ricinus communis    castor-oil plants                                         Saccharum officinarum                                                                             sugar cane                                                Sesamum indicum     sesame                                                    Solanum tuberosum   Irish potatoes                                            Sorghum bicolor (s. vulgare)                                                                      sorghum                                                   Sorghum dochna      sorgo                                                     Spinacia oleracea   spinach                                                   Theobroma cacao     cacao plants                                              Trifolium pratense  red clover                                                Triticum aestivum   wheat                                                     Vaccinium corymbosum                                                                              blueberries                                               Vaccinium vitis-idaea                                                                             cranberries                                               Vicia faba          tick beans                                                Vigna sinensis (V. unguiculata)                                                                   cow peas                                                  Vitis vinifera      grapes                                                     Zea mays           Indian corn, sweet                                                            corn, maize                                               ______________________________________                                    

To increase the spectrum of action and to achieve synergistic effects,the cyclohexenones of the formula I may be mixed with each other, andmixed and applied together with numerous representatives of otherherbicidal or growth-regulating active ingredient groups. Examples ofsuitable mixture components are diazines, 4H-3,1-benzoxazinederivatives, benzothiadiazinones, 2,6-dinitroanilines,N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines,amides, ureas, diphenyl ethers, triazinones, uracils, benzofuranderivatives, quinoline-carboxylic acids, cyclohexenones of a differentstructure, etc.

It may also be useful to apply the cyclohexenones of the formula I, orherbicidal agents containing them, either alone or in combination withother herbicides, in admixture with other crop protection agents, e.g.,agents for combating pests or phytopathogenic fungi or bacteria. Thecompounds may also be mixed with solutions of mineral salts used toremedy nutritional or trace element deficiencies. Non-phytotoxic oilsand oil concentrates may also be added.

We claim:
 1. A cyclohexenone of the formula ##STR9## where R¹ is C₁ -C₄-alkyl, R² is C₁ -C₄ -alkyl, C₃ -C₅ -alkynyl or unsubstituted orhalogen-substituted C₃ -C₅ -alkenyl, Z is hydrogen or C₂ -C₅-alkoxycarbonyl and X is an oxapentamethylene chain.
 2. A cyclohexenoneof the formula I as set forth in claim 1, where Z is hydrogen. 3.9-(1-Ethoxyimino-n-butyl)-3-oxaspiro[5,5]-undecane-8,10-dione.
 4. Aherbicide containing inert additives and an effective amount of acyclohexenone of the formula I as set forth in claim
 1. 5. A herbicideas set forth in claim 4, containing from 0.1 to 95 wt% of acyclohexenone of the formula I.
 6. A process for combatting the growthof unwanted plants, wherein the unwanted plants or the area to be keptfree from unwanted plant growth are treated with a herbicidallyeffective amount of a cyclohexenone of the formula I as set forth inclaim
 1. 7. A process as set forth in claim 6, wherein the cyclohexenoneof the formula I is applied at a rate of from 0.025 to 3 kg/ha.